JP5811985B2 - Adhesive composition - Google Patents

Description

  The present invention relates to an adhesive composition that forms a fluorine-containing elastomer after curing and adheres firmly to various substrates such as metals and plastics during curing. In particular, the present invention relates to an adhesive composition that can give a cured product having a smooth surface and a uniform surface in coating applications or potting applications.

  Conventionally, a curable fluorine-containing elastomer composition using an addition reaction between an alkenyl group and a hydrosilyl group is known, and an organopolysiloxane having a hydrosilyl group, an epoxy group, and / or a trialkoxysilyl group as a third component. There has been proposed a composition imparted with self-adhesive properties by adding (Patent Documents 1 and 2: Patent No. 3329717, Patent No. 3567973). The composition can be cured by heating for a short time, and the resulting cured product is excellent in solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, and electrical characteristics. Used in adhesive applications in various industrial fields where properties are required. In particular, it is frequently used as an adhesive sealant for electrical components in the automobile industry.

  However, the composition is useful as a durable adhesive sealant between the same or different materials using the stress relaxation of the elastomer. For example, the composition contains a coating on a substrate on which an electric / electronic element is mounted or an electric / electronic element. When applied to case potting, when the coating amount or casting amount increases, the surface of the cured product often becomes uneven and uneven, and there are dust, soot, water, corrosive substances, etc. in the dents. There is a problem in that the accumulation performance may become a starting point of the decomposition reaction, and the protection performance is not constant depending on the site. In order to solve this problem, the composition (Japanese Patent No. 3329717, Japanese Patent No. 3567973) is further combined with an epoxy group and / or trialkoxysilyl bonded to a nitrogen atom via a carbon atom in one molecule. Compositions containing isocyanurate compounds each having one or more groups have been proposed (Patent Documents 3 and 4: Japanese Patent Laid-Open Nos. 2005-002142 and 2007-126696). These compositions exhibit good adhesion to a wide variety of substrates such as metals and plastics, and can form a protective member having a smooth and uniform surface regardless of the thickness of the cured product. There is a drawback that the fluctuation range of the curing rate is large depending on the blending amount of the isocyanurate compound, and the curability deteriorates with storage time.

Japanese Patent No. 3329717 Japanese Patent No. 35679773 JP 2005-002142 A JP 2007-126696 A

  The present invention has been made in view of the above circumstances, and is excellent in solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, electrical characteristics, and a wide variety of substrates such as metals and plastics by heating in a short time. An object of the present invention is to provide an adhesive composition that exhibits good adhesion to a material, can give a cured product with a smooth surface and is excellent in curability and storage stability.

  As a result of intensive studies to achieve the above object, the present inventors have found that (A) a linear polymer having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. A fluoro compound, (B) a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to a silicon atom in one molecule, and (C) an addition reaction type curable composition comprising a platinum group metal hydrosilylation reaction catalyst , (D) hydrophobic silica powder, and (E) fluorine-containing acetylene alcohol, and (F) a hydrogen atom directly bonded to a silicon atom in one molecule and a silicon atom via a carbon atom or a carbon atom and an oxygen atom It has been found that a composition to which an organosiloxane having at least one epoxy group and / or trialkoxysilyl group each has been added can achieve the above-mentioned object. Which has led to be.

（式中、Ｒｆ ² は炭素数３〜１００のパーフルオロアルキル基で、途中にエーテル結合を含んでいてもよく、分岐していてもよい。Ｑは炭素数１〜６の２価の炭化水素基であり、Ｒ ³ 、Ｒ ⁴ 、Ｒ ⁵ は炭素数１〜４のアルキル基であり、同一又は異なっていてもよい。Ｔは炭素数１〜２０の２価の有機基である。）
（Ｆ）１分子中にケイ素原子に直結した水素原子と、炭素原子又は炭素原子と酸素原子を介してケイ素原子に結合したエポキシ基及び／又はトリアルコキシシリル基をそれぞれ１個以上有するオルガノシロキサン ０．１〜１０質量部
を含有することを特徴とする接着剤組成物。
〔２〕
（Ａ）成分が、下記一般式（１）：
ＣＨ₂＝ＣＨ−（Ｘ）_a−Ｒｆ¹−（Ｘ’）_a−ＣＨ＝ＣＨ₂ （１）
［式中、Ｘは−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ¹−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（Ｚ）

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基、Ｒ¹は水素原子、非置換もしくは置換の１価炭化水素基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（Ｚ’）

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²は上記Ｒ¹と同じ基である。Ｒｆ¹は下記一般式（ｉ）又は（ｉｉ）

（式中、ｐ及びｑはそれぞれ１〜１５０の整数であって、かつｐとｑの和の平均は、２〜２００である。またｒは０〜６の整数、ｔは２又は３である。）

（式中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは上記と同じである。）
で表される２価のパーフルオロポリエーテル基である。ａは独立に０又は１である。］
で表される分岐を有する直鎖状ポリフルオロ化合物である〔１〕記載の接着剤組成物。
〔３〕
（Ｂ）成分の含フッ素オルガノ水素シロキサンが、１分子中に１個以上の１価のパーフルオロアルキル基、１価のパーフルオロオキシアルキル基、２価のパーフルオロアルキレン基、又は２価のパーフルオロオキシアルキレン基を有するものである〔１〕又は〔２〕記載の接着剤組成物。
〔４〕
（Ｆ）成分のオルガノシロキサンが、更に炭素原子又は炭素原子と酸素原子を含む２価の連結基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基を１個以上有するものである〔１〕〜〔３〕のいずれかに記載の接着剤組成物。 Therefore, this invention provides the adhesive composition shown below.
[1]
(A) 100 parts by mass of a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain;
(B) Fluorinated organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule (A) 0.5 to 3.0 moles as Si-H groups per mole of alkenyl groups in component (A) The amount,
(C) Platinum group metal hydrosilylation catalyst
0.1 to 500 ppm in terms of platinum group metal atoms,
(D) 0.5-30 parts by mass of hydrophobic silica powder,
(E) Fluorine-containing acetylene alcohol represented by the following general formula (2) or (3)
0.05-3.0 parts by mass,

(In the formula, Rf ² is a C 3-100 perfluoroalkyl group which may contain an ether bond in the middle or may be branched. Q is a C 1-6 divalent hydrocarbon. R ³ , R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms, which may be the same or different, and T is a divalent organic group having 1 to 20 carbon atoms.
(F) Organosiloxane having one or more hydrogen atoms directly bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms in one molecule. .1-10 parts by mass of an adhesive composition,
[2]
The component (A) is represented by the following general formula (1):
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- (Y is -CH ₂ - or the following structural formula (Z)

O, m or a p-dimethylsilylphenylene group represented by formula (I), R ¹ is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (Y ′ is —CH ₂ — or the following structural formula (Z ′)

O, m or p-dimethylsilylphenylene group represented by formula (I), and R ² is the same group as R ¹ described above. Rf ¹ represents the following general formula (i) or (ii)

(In the formula, p and q are each an integer of 1 to 150, and the average of the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3. .)

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)
It is a bivalent perfluoropolyether group represented by these. a is independently 0 or 1. ]
The adhesive composition according to [1], which is a linear polyfluoro compound having a branch represented by the formula:
[3]
The component (B) fluorine-containing organohydrogensiloxane is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoroalkyl group in one molecule. The adhesive composition according to [1] or [2], which has a fluorooxyalkylene group.
[ 4 ]
The (F) component organosiloxane further has a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom. The adhesive composition according to any one of [1] to [ 3 ], which has one or more.

  According to the adhesive composition of the present invention, it has excellent solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, electrical characteristics, and a wide range of metals, plastics, etc. by relatively low temperature and short time heating. A cured product having good adhesion to various types of substrates can be provided. In particular, it can provide a cured product with a smooth surface and excellent curability and storage stability, so it can be used in coating and potting applications for electrical and electronic parts that require long-term protection performance. It can be preferably used.

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基、Ｒ¹は水素原子、非置換もしくは置換の１価炭化水素基、Ｘ’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（Ｚ’）

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²は上記Ｒ¹と同じ基である。Ｒｆ¹は２価のパーフルオロポリエーテル基であり、ａは独立に０又は１である。］ Hereinafter, the present invention will be described in more detail.
[Component (A)]
(A) component of this invention is a linear polyfluoro compound which has a 2 or more alkenyl group in 1 molecule, and what is represented by following General formula (1) is preferable.
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- (Y is -CH ₂ - or the following structural formula (Z)

O, m or a p-dimethylsilylphenylene group represented by formula (I), R ¹ is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (Y ′ is —CH ₂ — or the following structural formula (Z ′)

O, m or p-dimethylsilylphenylene group represented by formula (I), and R ² is the same group as R ¹ described above. Rf ¹ is a divalent perfluoropolyether group, and a is independently 0 or 1. ]

Here, as R ¹ and R ² , in the case of other than a hydrogen atom, those having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms are preferred, and specifically, methyl group, ethyl group, propyl group, butyl group, hexyl Group, cyclohexyl group, alkyl group such as octyl group; aryl group such as phenyl group, tolyl group; aralkyl group such as benzyl group, phenylethyl group, etc., or part or all of hydrogen atoms of these groups such as fluorine Examples thereof include a substituted monovalent hydrocarbon group substituted with a halogen atom.

Here, Rf ¹ in the above general formula is a divalent perfluoropolyether group, and a group represented by the following general formula (i) or (ii) is preferable.

（式中、ｐ及びｑはそれぞれ１〜１５０の整数、好ましくは１０〜１００の整数であって、かつｐとｑの和の平均は、２〜２００、好ましくは２０〜１６０である。またｒは０〜６の整数、好ましくは０〜４の整数であり、ｔは２又は３である。）

(Wherein p and q are each an integer of 1 to 150, preferably an integer of 10 to 100, and the average of the sum of p and q is 2 to 200, preferably 20 to 160. r Is an integer of 0-6, preferably 0-4, and t is 2 or 3.)

（式中、ｕは１〜２００の整数、好ましくは２０〜１６０の整数であり、ｖは１〜５０の整数、好ましくは５〜４０の整数であり、ｔは上記と同じである。）

(In the formula, u is an integer of 1 to 200, preferably 20 to 160, v is an integer of 1 to 50, preferably 5 to 40, and t is the same as above.)

Preferred examples of the Rf ¹ group include the following three groups. More preferably, it is a divalent group having the structure of the first formula.

（式中、ｐ１及びｑ１はそれぞれ１〜１５０の整数、ｐ１＋ｑ１（平均）＝２〜２００であり、Ｌは２〜６の整数である。）

(Wherein p1 and q1 are each an integer of 1 to 150, p1 + q1 (average) = 2 to 200, and L is an integer of 2 to 6)

（式中、ｐ２及びｑ２はそれぞれ１〜１５０の整数、ｐ２＋ｑ２（平均）＝２〜２００であり、Ｌは２〜６の整数である。）

(Wherein, p2 and q2 are each an integer of 1 to 150, p2 + q2 (average) = 2 to 200, and L is an integer of 2 to 6)

（式中、ｕ１は１〜２００の整数、ｖ１は１〜５０の整数である。）

(In the formula, u1 is an integer of 1 to 200, and v1 is an integer of 1 to 50.)

［式中、Ｘ¹は−ＣＨ₂−、−ＣＨ₂Ｏ−、−ＣＨ₂ＯＣＨ₂−又は−Ｙ−ＮＲ²¹−ＣＯ−（Ｙは−ＣＨ₂−又は下記構造式（Ｚ）

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基、Ｒ²¹は水素原子、メチル基、フェニル基又はアリル基、Ｘ¹’は−ＣＨ₂−、−ＯＣＨ₂−、−ＣＨ₂ＯＣＨ₂−又は−ＣＯ−ＮＲ²²−Ｙ’−（Ｙ’は−ＣＨ₂−又は下記構造式（Ｚ’）

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ²²は上記Ｒ²¹と同じである。ａは独立に０又は１、Ｌは２〜６の整数、ｐ３及びｑ３はそれぞれ１〜１５０の整数、かつｐ３＋ｑ３（平均）＝２〜２００である。］ Preferable examples of the component (A) include compounds represented by the following general formula (4).

Wherein, X ¹ is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ²¹ -CO- (Y is -CH ₂ - or the following structural formula (Z)

O, m or p-dimethylsilylphenylene group represented by formula (I), R ²¹ is a hydrogen atom, methyl group, phenyl group or allyl group, X ¹ ′ is —CH ₂ —, —OCH ₂ —, — CH ₂ OCH ₂ — or —CO—NR ²² —Y′— (Y ′ is —CH ₂ — or the following structural formula (Z ′)

O, m or p-dimethylsilylphenylene group represented by formula (I), and R ²² is the same as R ²¹ described above. a is independently 0 or 1, L is an integer of 2 to 6, p3 and q3 are each an integer of 1 to 150, and p3 + q3 (average) = 2 to 200. ]

  Specific examples of the linear polyfluoro compound represented by the general formula (1) include those represented by the following formula.

（式中、ｐ’及びｑ’はそれぞれ１〜１５０の整数、ｐ’＋ｑ’＝２〜２００を満足する整数を示す。）

(In the formula, p ′ and q ′ each represent an integer satisfying 1 to 150 and p ′ + q ′ = 2 to 200).

  In addition, the viscosity (23 degreeC) by the rotational viscometer of the linear polyfluoro compound of the said General formula (1) is 100-100,000 mPa * s, More preferably, it is 500-50,000 mPa * s, More preferably, it is 1 In the case of using this composition for sealing, coating, potting, impregnation, etc., it is desirable that the cured product has appropriate physical properties. . Within the viscosity range, the most appropriate viscosity can be selected according to the application.

  In addition, the linear polyfluoro compound of component (A) has a number average molecular weight of 1 in terms of polystyrene in gel permeation chromatography (GPC) analysis (solvent: 1,3-bis (trifluoromethyl) benzene). 3,000 to 35,000, preferably 4,000 to 30,000. If the number average molecular weight is too small, the resulting cured product may be brittle and easily cracked. If the number average molecular weight is too large, the fluidity of the composition may deteriorate, and the physical strength of the resulting cured product may also decrease. .

  The amount of alkenyl group contained in the linear polyfluoro compound represented by the general formula (1) is preferably 0.0070 to 0.0500 mol / 100 g, more preferably 0.0080 to 0.0400 mol / 100 g. is there. If the amount of alkenyl groups contained in the linear polyfluoro compound is too small, the physical strength of the resulting cured product may be reduced, and if the amount of alkenyl groups is too large, the resulting cured product may be brittle and easily cracked.

  These linear polyfluoro compounds can be used singly or in combination of two or more.

[(B) component]
The component (B) has 2 or more, preferably 1 to 10 fluorine-containing organic groups in one molecule, and 2 hydrogen atoms (that is, a hydrosilyl group represented by Si—H) directly bonded to a silicon atom. It is a fluorine-containing organohydrogensiloxane having at least 1, preferably 3-50. The component (B) of the present invention functions as a crosslinking agent and / or chain extender of the component (A), and is compatible with the component (A), dispersibility, and uniformity after curing. In view of the above, as the fluorine-containing organic group, one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoro group in one molecule Those having a fluorine-containing group such as an oxyalkylene group are preferred.

（式中、ｆは１〜２００の整数、好ましくは１〜１００の整数、ｈは１〜３の整数である。）

（式中、ｉ及びｊはそれぞれ１以上の整数、好ましくは１〜１００の整数、ｉ＋ｊの平均は２〜２００、好ましくは２〜１００である。）
−（ＣＦ₂Ｏ）_d−（ＣＦ₂ＣＦ₂Ｏ）_e−ＣＦ₂−
（但し、ｄ及びｅはそれぞれ１〜５０の整数、好ましくは１〜４０の整数である。） Examples of the monovalent or divalent fluorine-containing organic group include those represented by the following general formula.
C _g F _{2g + 1} −
−C _g F _2g −
(In the formula, g is an integer of 1 to 20, preferably an integer of 2 to 10.)

(In the formula, f is an integer of 1 to 200, preferably an integer of 1 to 100, and h is an integer of 1 to 3.)

(In the formula, i and j are each an integer of 1 or more, preferably an integer of 1 to 100, and the average of i + j is 2 to 200, preferably 2 to 100.)
_{- (CF 2 O) d -} (CF 2 CF 2 O) e -CF 2 -
(However, d and e are each an integer of 1 to 50, preferably an integer of 1 to 40.)

The perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group and the silicon atom are preferably connected by a divalent linking group, and as the divalent linking group, May be an alkylene group, an arylene group and a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, an ester bond, a diorganosilylene group or the like interposed between these groups.
-CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ -,
_{-CH 2 CH 2 CH 2 OCH 2} -,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 2 CH 3) -CO-,
_{-CH 2 CH 2 -Si (CH 3} ) 2 -Ph'-N (CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -Si (} CH 3) 2 -Ph'-N (CH 3) -CO-,
—CH ₂ CH ₂ CH ₂ —O—CO—
(However, Ph is a phenyl group, and Ph ′ is a phenylene group.)
C2-C12 bivalent coupling groups, such as, etc. are mentioned.

  In addition, as the monovalent substituent bonded to the silicon atom other than the monovalent or divalent fluorine-containing organic group and the hydrogen atom bonded to the silicon atom in the fluorine-containing organohydrogensiloxane of the component (B), for example, Alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group and decyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group and naphthyl group An aralkyl group such as a benzyl group or a phenylethyl group and a hydrogen atom of these groups partially or entirely substituted with a chlorine atom, a cyano group, or the like, for example, a carbon such as a chloromethyl group, a chloropropyl group, or a cyanoethyl group Examples thereof include an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20, preferably 1 to 12.

  The fluorine-containing organohydrogensiloxane as the component (B) may be any of cyclic, chain, three-dimensional network, and combinations thereof. The number of silicon atoms in the fluorine-containing organohydrogenpolysiloxane is not particularly limited, but is usually 2 to 60, preferably about 3 to 30.

  Examples of the component (B) having such a monovalent or divalent fluorine-containing organic group and a silicon atom-bonded hydrogen atom include the following compounds. These compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.

  The amount of Si—H groups contained in the fluorine-containing organohydrogensiloxane as the component (B) is preferably 0.00050 to 0.01000 mol / g, more preferably 0.00100 to 0.00800 mol / g. If the amount of Si-H groups contained in the fluorinated organohydrogensiloxane is too small, the physical properties of the resulting cured product may be deteriorated due to insufficient crosslinking density. If the amount of Si-H groups is too large, foaming may occur during curing. Or the physical properties of the resulting cured product may change significantly over time.

  These fluorine-containing organohydrogensiloxanes can be used alone or in combination of two or more.

  The blending amount of the component (B) is the hydrosilyl group in the component (B), that is, the Si-H group, with respect to 1 mol of alkenyl groups such as vinyl group, allyl group, cycloalkenyl group and the like contained in the component (A) Is 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol. If the amount of hydrosilyl groups (≡Si—H) is too small, the crosslink density becomes insufficient. As a result, a cured product cannot be obtained.

[Component (C)]
The component (C) of the present invention is a platinum group metal hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). Since this hydrosilylation reaction catalyst is generally a noble metal compound and is expensive, platinum or platinum compounds that are relatively easily available are often used.

Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinyl siloxane, metal platinum supported on silica, alumina, carbon or the like. Rhodium, ruthenium, iridium and palladium compounds are also known as platinum group metal catalysts other than platinum compounds. For example, RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like can be exemplified. In the above formula, Ph is a phenyl group.

  When these catalysts are used, they can be used in solid form when they are solid catalysts, but in order to obtain a more uniform cured product, chloroplatinic acid or a complex dissolved in an appropriate solvent. Is preferably used by being dissolved in the linear polyfluoro compound of component (A).

  (C) The usage-amount of a component is 0.1-500 ppm in conversion of a platinum group metal atom with respect to 100 mass parts of (A) component, Preferably it is 1-100 ppm.

[Component (D)]
The component (D) of the present invention is a hydrophobic silica powder, and at the same time imparts appropriate physical strength to the cured product obtained from the composition of the present invention, and at the same time the organosiloxane of the component (F) described later. It has an action of uniformly dispersing in it. As the hydrophobic silica powder of component (D), a known BET specific surface area as silicone rubber filler 50 m ² / g or more, particularly 50 to 400 m ² / g preferably those treated hydrophobic fine powder silica It is.

When the BET specific surface area is less than 50 m ² / g, the resulting cured product has insufficient physical strength, and the component (F) may not be uniformly dispersed. If it exceeds 400 m ² / g, the kneading operation becomes difficult, and the dispersion of component (D) may become non-uniform. Examples of the fine powder silica include fumed silica, precipitated silica, colloidal silica, and the like. Among these, fumed silica is most preferable.

  Examples of the hydrophobizing agent for fine powder silica include organochlorosilane, organodisilazane, cyclic organopolysilazane, linear organopolysiloxane, etc. Among them, organochlorosilane, organodisilazane, cyclic organo Polysilazane is preferred.

  The compounding amount of the component (D) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the component (A), and is preferably in the range of 1 to 25 parts by mass. If the blending amount is less than 0.5 parts by mass, the physical properties of the resulting cured product are lowered and the adhesiveness becomes unstable. On the other hand, when it exceeds 30 mass parts, the fluidity | liquidity of a composition will worsen and the physical strength of the hardened | cured material obtained will fall on the contrary.

[(E) component]
The fluorine-containing acetylene alcohol which is the component (E) of the present invention acts as a control agent for the hydrosilylation reaction. By adding this, the composition of the present invention is imparted with appropriate curability and storage stability. In order to impart good adhesion and flat surface properties to the cured product obtained from the composition. The component is acetylene alcohol containing a perfluoroalkyl group, and the perfluoroalkyl group may contain an ether bond or may be branched, but is represented by the following general formula (2) or (3) Is preferred.

（式中、Ｒｆ²は炭素数３〜１００のパーフルオロアルキル基で、途中にエーテル結合を含んでいてもよく、分岐していてもよい。Ｑは炭素数１〜６の２価の炭化水素基であり、Ｒ³、Ｒ⁴、Ｒ⁵は炭素数１〜４のアルキル基であり、同一又は異なっていてもよい。Ｔは炭素数１〜２０の２価の有機基である。）

(In the formula, Rf ² is a C 3-100 perfluoroalkyl group which may contain an ether bond in the middle or may be branched. Q is a C 1-6 divalent hydrocarbon. R ³ , R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms, which may be the same or different, and T is a divalent organic group having 1 to 20 carbon atoms.

In the above formulas (2) and (3), examples of Rf ² include the following structures.

Q is a C 1-6 divalent hydrocarbon group, and specific examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an isobutylene group, and a phenylene group. Among these, a methylene group and an ethylene group are preferable.
R ³ , R ⁴ and R ⁵ are each an alkyl group having 1 to 4 carbon atoms which may be the same or different, and specifically include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, isobutyl group, tert-butyl group and the like. R ³ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Moreover, as R < ⁴ >, R < ⁵ >, a methyl group and n-butyl group are preferable.

（式中、Ｒ⁶及びＲ⁷はそれぞれ炭素数１〜９のアルキル基もしくは水素原子である。アルキル基として、具体的には、メチル基、エチル基、プロピル基、フェニル基、シクロヘキシル基等が挙げられる。）

（式中、ｂ、ｃはそれぞれ０又は１〜４の整数であり、好ましくは０，１又は２である。） Here, T is a C1-C20 divalent organic group. T is not particularly limited as long as it is a divalent organic group having 1 to 20 carbon atoms, but may have an oxygen atom, a nitrogen atom, a carbonyl group, or the like on the way, and examples thereof include the following structures.
− (CH ₂ ) _M −
(In the formula, M is an integer of 1 to 10, preferably an integer of 2 to 4.)
_{- (CH 2) -O- (CH} 2) N -
(In the formula, N is an integer of 1 to 9, preferably an integer of 2 to 4.)

(In the formula, R ⁶ and R ⁷ are each an alkyl group having 1 to 9 carbon atoms or a hydrogen atom. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a phenyl group, and a cyclohexyl group. Can be mentioned.)

(In the formula, b and c are each 0 or an integer of 1 to 4, preferably 0, 1 or 2.)

  Specific examples of the fluorine-containing acetylene alcohol used as the component (E) include those represented by the following structural formula.

  (E) The compounding quantity of a component is 0.05-3.0 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 0.1-2.0 mass parts. When the amount is less than 0.05 parts by mass, the storage stability with time is inferior and the adhesiveness is also insufficient. On the other hand, if it exceeds 3.0 parts by mass, the curability is inhibited and the physical properties of the resulting cured product are reduced.

[(F) component]
The organosiloxane which is the component (F) of the present invention is for fully expressing the self-adhesiveness in the composition of the present invention by blending it. The organosiloxane is an organo having one or more hydrogen atoms directly bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms in one molecule. Siloxane, and preferably one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom. It is an organosiloxane having the above.

  The siloxane skeleton of the organosiloxane may be any of cyclic, chain, branched, etc., or a mixed form thereof. As the organosiloxane which is the component (F) of the present invention, those represented by the following average composition formula can be used.

（式中、Ｒ⁸は独立に非置換又はハロゲン置換の１価炭化水素基であり、Ａ、Ｂは下記に示す。ｗは０≦ｗ≦１００、ｘは１≦ｘ≦１００、ｙは１≦ｙ≦１００、ｚは０≦ｚ≦１００を示す。）

(In the formula, R ⁸ is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group, A and B are shown below. W is 0 ≦ w ≦ 100, x is 1 ≦ x ≦ 100, and y is 1. <= Y <= 100 and z shows 0 <= z <= 100.)

In the above formula, the unsubstituted or halogen-substituted monovalent hydrocarbon group for R ⁸ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, Alkyl groups such as butyl group, hexyl group, cyclohexyl group and octyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group; and part or all of hydrogen atoms of these groups A substituted monovalent hydrocarbon group in which is substituted with a halogen atom such as fluorine, and the like. Among them, a methyl group is particularly preferable.

  w is preferably 0 ≦ w ≦ 20, x is preferably 1 ≦ x ≦ 20, y is preferably 1 ≦ y ≦ 20, z is preferably 1 ≦ z ≦ 20, and is preferably 3 ≦ w + x + y + z ≦ 50.

  A represents an epoxy group and / or a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples thereof include the following groups.

（式中、Ｒ⁹は酸素原子が介在してもよい炭素数１〜１０、特に１〜５の２価炭化水素基で、具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、オクチレン基等のアルキレン基、シクロへキシレン基等のシクロアルキレン基、オキシエチレン基、オキシプロピレン基、オキシブチレン基等のオキシアルキレン基などを示す。）

(In the formula, R ⁹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms in which an oxygen atom may intervene, specifically, a methylene group, an ethylene group, a propylene group, a butylene group, An alkylene group such as a hexylene group and an octylene group, a cycloalkylene group such as a cyclohexylene group, an oxyalkylene group such as an oxyethylene group, an oxypropylene group, and an oxybutylene group.

-R ¹⁰ -Si (OR ¹¹ ) ₃
(In the formula, R ¹⁰ is a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, particularly 1 to 4 carbon atoms. Specifically, methylene group, ethylene group, propylene group, butylene group, hexylene group, cyclohexylene group, Represents an alkylene group such as an octylene group, and R ¹¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, An alkyl group such as an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group is shown.)

（式中、Ｒ¹²は独立に炭素数１〜８、特に１〜４の１価炭化水素基であり、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等のアルキル基などを示し、Ｒ¹³は水素原子又はメチル基であり、ｋは２〜１０の整数、好ましくは２〜６の整数を示す。）

(In the formula, R ¹² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. And an alkyl group such as an isobutyl group and a tert-butyl group, R ¹³ is a hydrogen atom or a methyl group, and k is an integer of 2 to 10, preferably an integer of 2 to 6.)

Specific examples of A include those shown below.

（式中、ｆ、ｈは上記と同じである。） B represents a monovalent perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom. Examples of the monovalent perfluoroalkyl group or perfluorooxyalkyl group include those represented by the following general formula.
C _g F _{2g + 1} −
(Wherein g is the same as above)

(Wherein f and h are the same as above)

The divalent linking group containing a carbon atom or a carbon atom and an oxygen atom includes an alkylene group, an arylene group and a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, etc. interposed in these groups. There may be, for example,
-CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ -,
_{-CH 2 CH 2 CH 2 OCH 2} -,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO-
(However, Ph is a phenyl group.)
C2-C12 bivalent coupling groups, such as, etc. are mentioned.

（但し、Ｐｈはフェニル基である。） Specific examples of B include those shown below.

(However, Ph is a phenyl group.)

  These organosiloxanes are composed of organohydrogenpolysiloxane having 3 or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, aliphatic unsaturated groups such as vinyl groups and allyl groups, epoxy groups, and / or Alternatively, a compound containing a trialkoxysilyl group and, if necessary, a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or perfluorooxyalkyl group can be obtained by partial addition reaction according to a conventional method. . Note that the number of the aliphatic unsaturated groups needs to be smaller than the number of Si-H groups.

  In the production of the organosiloxane in the present invention, the target substance may be isolated after completion of the reaction, but a mixture in which only the unreacted substance and the addition reaction catalyst are removed can also be used.

  Specific examples of the organosiloxane used as the component (F) include those represented by the following structural formula. In addition, these compounds may be used independently and may use 2 or more types together. Note that Me is a methyl group and Ph is a phenyl group.

（式中、ｘ１は１〜８、ｙ１は１〜３、ｗ１は１〜４、ｙ２は１〜３である。）

(In the formula, x1 is 1 to 8, y1 is 1 to 3, w1 is 1 to 4, and y2 is 1 to 3.)

（式中、ｘ３は１〜８、ｗ２は１〜４、ｚ２は１〜３、ｙ４は１〜３である。）

(In the formula, x3 is 1 to 8, w2 is 1 to 4, z2 is 1 to 3, and y4 is 1 to 3.)

  (F) The usage-amount of a component is 0.1-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.2-5 mass parts. When the amount is less than 0.1 parts by mass, sufficient adhesiveness cannot be obtained. When the amount exceeds 10 parts by mass, the fluidity of the composition is deteriorated, the physical strength of the resulting cured product is lowered, and the curability is reduced. May interfere.

[Other ingredients]
In the composition of the present invention, in addition to the above components (A) to (F), in order to enhance its practicality, a plasticizer, a viscosity modifier, a flexibility imparting agent, an inorganic filler, an adhesion promoter, Various compounding agents such as an adhesion aid other than the component (F) and a silane coupling agent can be added as necessary. The blending amount of these additives is arbitrary as long as the object of the present invention is not impaired and the properties of the composition and the physical properties of the cured product are not impaired.

  As a plasticizer, a viscosity modifier, and a flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following general formula (5) and / or a linear poly represented by the following general formulas (6) and (7) A fluoro compound can be used in combination.

（式中、ｆ１は１以上の整数、好ましくは２〜１００の整数であり、ｔは上記と同じであり、かつ上記（Ａ）成分のＲｆ¹基に関するｐ＋ｑ（平均）及びｒの和、並びにｕ及びｖの和のいずれの和よりも小さい。）］ Rf ³ − (X ′) _a CH═CH ₂ (5)
[Wherein, X ′ and a are the same as described above, and Rf ³ is the following general formula (iii).

(Wherein f1 is an integer of 1 or more, preferably an integer of 2 to 100, t is the same as above, and the sum of p + q (average) and r for the Rf ¹ group of the component (A), and smaller than any sum of u and v)]]

_{D-O- (CF 2 CF 2} CF 2 O) c1 -D (6)
(In the formula, D is a group represented by the formula: C _s F _{2s + 1} — (s is 1 to 3), c1 is an integer of 1 to 200, preferably an integer of 2 to 100, and (It is smaller than the sum of p + q (average) and r and the sum of u and v with respect to the Rf ¹ group of the component (A).)
_{D-O- (CF 2 O)} d1 (CF 2 CF 2 O) e1 -D (7)
(Wherein D is the same as above, d1 and e1 are each an integer of 1 to 200, preferably an integer of 1 to 100, and the sum of d1 and e1 is the Rf ^{1 of the} component (A)) Less than or equal to the sum of p + q (average) and r for the group, and the sum of u and v.)

  Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (5) include, for example, the following compounds (note that f1 'below satisfies the above requirements).

Specific examples of the linear polyfluoro compound represented by the general formulas (6) and (7) include, for example, the following (the following c1 ′ and the sum of d1 ′ and e1 ′ are Satisfying the above requirements).
_{CF 3 O- (CF 2 CF 2} CF 2 O) c1 '-CF 2 CF 3
_{CF 3 - [(OCF 2 CF} 2) e1 '(OCF 2) d1'] -O-CF 3
(In the formula, c1 ′ is an integer of 1 to 200, d1 ′ is an integer of 1 to 200, e1 ′ is an integer of 1 to 200, and d1 ′ + e1 ′ = 2 to 200.)

  The compounding amount of the compounds of the above formulas (5) to (7) is 1 to 300 parts by mass with respect to 100 parts by mass of the component (A) in the composition, particularly the polyfluorodialkenyl compound of the above formula (1) Preferably it is 50-250 mass parts. Further, the viscosity (23 ° C.) by the rotational viscometer is desirably in the range of 5 to 100,000 mPa · s for the same reason as that of the polyfluorodialkenyl compound.

  As inorganic fillers, for example, reinforcing or semi-reinforcing fillers such as quartz powder, fused quartz powder, diatomaceous earth, calcium carbonate, inorganic pigments such as titanium oxide, iron oxide, carbon black, cobalt aluminate, titanium oxide, oxidation Heat improver such as iron, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate, thermal conductivity imparting agent such as alumina, boron nitride, silicon carbide, metal powder, carbon black, silver powder, A conductivity-imparting agent such as conductive zinc white can be added.

  Moreover, adhesion promoters and / or silane coupling agents other than (F) component, adhesion promoters, such as carboxylic acid anhydride and a titanic acid ester, can be added.

[Adhesive composition]
In the adhesive composition of the present invention, the above-described components (A) to (F) and other optional components are mixed with a mixing device such as a planetary mixer, a loss mixer, a Hobart mixer, a kneader, a three-roll, etc. It can manufacture by mixing uniformly using this kneading apparatus.

  The manufacturing method in particular of the adhesive composition of this invention is not restrict | limited, It can manufacture by kneading the said component. Two compositions may be mixed at the time of use.

  In the method for producing a perfluoropolyether-based adhesive composition containing the above-described components of the present invention, the component (D) is first heated or unheated in the range of 20 to 60 parts by mass with respect to 100 parts by mass of the component (A). It is blended under the conditions, kneaded under heating / depressurization conditions, or heating / pressurization conditions, and then post-diluted with the component (A) so as to obtain a predetermined blending ratio. The adhesive properties of the fluoropolyether adhesive composition can be improved.

  In the blending and kneading of the component (A) and the component (D), the surface of the hydrophobic silica powder as the component (D) is sufficiently covered with the linear polyfluoro compound as the component (A), and (B) And (F) the kneading apparatus such as planetary mixer, gate mixer and kneader for reducing the viscosity of the adhesive composition and improving the adhesive properties by making the component difficult to be adsorbed on the silica surface. Etc.

  The compounding ratio of the component (A) and the component (D) varies depending on the type of the hydrophobic silica powder as the component (D), but the component (D) is 20 to 60 masses per 100 parts by mass of the component (A). If it is less than 20 parts by mass, it is difficult to reduce the viscosity of the final blended composition, and the viscosity becomes very high. On the other hand, when the amount exceeds 60 parts by mass, heat generation during kneading becomes intense, the mechanical properties of the composition are lowered, and it is difficult to mix the powder with a machine.

  The temperature and time for blending and kneading are not particularly limited, but are performed to stabilize physical properties such as mechanical properties of the adhesive composition. The heat treatment temperature is 120 to 180 ° C., and it is preferably performed for 1 hour or longer in order to perform uniform kneading.

  The pressure at the time of blending and kneading varies depending on the apparatus used, but it is essential to carry out under pressure or reduced pressure depending on the apparatus. For example, a planetary mixer or a gate mixer is kneaded under reduced pressure, and the pressure is preferably -0.05 MPa or less as a gauge pressure, and a kneader is kneaded under pressure, and the pressure is 0.4 to 0 as a gauge pressure. .6 MPa is preferable. The operation is performed under these conditions because the component (A) easily wets (is easy to coat) the surface of the component (D).

  By blending the above components (A), (B), (C), (E) and (F) with the liquid base comprising the components (A) and (D) obtained as described above, A fluoropolyether adhesive composition can be obtained.

  The produced adhesive composition is cured at room temperature according to the type and amount of the functional group of the linear polyfluoro compound of component (A), the type and amount of catalyst of component (C), and the type and amount of component (E). However, in order to promote curing, heating is preferable, and in order to exhibit good adhesion particularly to various substrates, 60 ° C. or higher, preferably 100 to 200 ° C. for several minutes. It is preferable to cure in about several hours.

  In using the adhesive composition of the present invention, an appropriate fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, Fluorinert (manufactured by 3M Co., Ltd.) is used depending on its use and purpose. ), Perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluoropolyether oligomer, or a mixture thereof may be used after being dissolved in a desired concentration. In particular, it is preferable to use a solvent in thin film coating applications.

  The adhesive composition of the present invention is useful as an adhesive for automobile-related parts and various electric / electronic parts. For example, it is suitable as an adhesive sealant, protective coating agent, and potting agent for detectors and sensors such as various pressure sensors, gas concentration detectors, and temperature sensors used in automobile control systems. Protective sealants for sensors exposed to chemicals, adhesives for ink jet printers, adhesives and sealants for printer heads, coating agents for rolls and belts in laser printers and copying machines, various circuit boards It can be suitably used for adhesive sealants, coating agents, potting agents and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part. Further, the viscosity, adhesive force, and the like are measured values at 23 ° C. (based on JIS K6249).

[Example 1]
60 parts of a polymer represented by the following formula (8) (viscosity 10,000 mPa · s, number average molecular weight 16,700, vinyl group content 0.012 mol / 100 g) is charged in a planetary mixer, and the internal temperature is 50-100. While maintaining the temperature at 18 ° C., 18 parts of fumed silica (BET specific surface area 110 m ² / g) surface-treated with dimethyldichlorosilane was added in portions. Thereafter, heating was stopped and kneading was performed under reduced pressure (gauge pressure; -0.093 MPa) for 1 hour. Subsequently, the apparatus was heated while kneading, and after the internal temperature reached 130 ° C., heat treatment was performed under reduced pressure (gauge pressure: −0.093 MPa) for 3 hours while maintaining the temperature at 130 to 160 ° C. Next, after the content was cooled to 40 ° C. or lower, 40 parts of a polymer represented by the following formula (8) was added and kneaded for 30 minutes under reduced pressure (gauge pressure; −0.093 MPa). The contents were taken out and passed through three rolls twice to obtain a base compound.

  Further, 25 parts of a solid carboxylic acid anhydride represented by the following formula (9) and 75 parts of a polymer represented by the following formula (8) were charged into a planetary mixer, mixed at room temperature for 30 minutes, and further reduced in pressure for 30 minutes. (Gauge pressure; -0.093 MPa). This mixture was taken out and passed through three rolls twice to obtain a carboxylic anhydride paste.

  To 29.5 parts of the base compound, 75.0 parts of a polymer represented by the following formula (8) and 0.8 part of the carboxylic acid anhydride paste were charged in a planetary mixer and mixed until uniform. To this, 0.20 part of a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration: 0.5% by mass) and 0.45 part of fluorinated acetylene alcohol represented by the following formula (10) are added to make uniform. Until mixed. Next, 1.8 parts of fluorine-containing organohydrogensiloxane represented by the following formula (11) (Si-H group amount 0.00394 mol / g), 1.2 parts of fluorine-containing organohydrogensiloxane represented by the following formula (12) (Si—H group amount 0.00722 mol / g) and 2.5 parts of an adhesion-imparting agent represented by the following formula (13) were sequentially added and mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

  After filling the obtained composition into a cartridge container, it was extruded onto a flat plate made of tetrafluoroethylene (50 mm × 50 mm × 2 mm) and applied using a bar coater so that the thickness of the composition layer was 250 μm. The tetrafluoroethylene flat plate coated with the above composition was cured by heating for 1 hour in a drier set at 150 ° C. Moreover, after inject | pouring the said composition into a glass petri dish (inner diameter 32mm, depth 15mm) so that thickness may be set to 2 mm, the said glass petri dish was heated and hardened in the dryer set to 150 degreeC for 1 hour. . Table 1 shows the observation results of the surface of each cured product.

Regarding the curability immediately after the preparation of the above composition and after storage at 40 ° C. for 3 weeks, the T ₉₀ value when heated at 150 ° C. for 1 hour was measured using a rheometer (MDR2000 manufactured by Alpha Technologies) (JIS). According to K6300-2). Each measurement result is shown in Table 1.

  Next, 50 mm × 25 mm test panels of various adherends listed in Table 2 are stacked with a composition layer having a thickness of 80 μm so that each end overlaps by 10 mm, and heated at 150 ° C. for 1 hour. Thus, the composition was cured to prepare an adhesion test piece. Subsequently, these samples were subjected to a tensile shear adhesion test (tensile speed: 50 mm / min) to evaluate the adhesive strength and the cohesive failure rate. The results are shown in Table 2.

[Example 2]
The same method as in Example 1 except that 0.65 part of the fluorinated acetylene alcohol represented by the following formula (14) was used instead of 0.45 part of the fluorinated acetylene alcohol represented by the formula (10) in Example 1. A composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 3]
The same method as in Example 1, except that 0.40 part of the fluorinated acetylene alcohol represented by the following formula (15) was used instead of 0.45 part of the fluorinated acetylene alcohol represented by the formula (10) in Example 1. A composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 4]
The same method as in Example 1, except that 0.60 part of the fluorinated acetylene alcohol represented by the following formula (16) was used instead of 0.45 part of the fluorinated acetylene alcohol represented by the formula (10) in Example 1. A composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 5]
The same method as in Example 1 except that 0.50 part of the fluorinated acetylene alcohol represented by the following formula (17) was used instead of 0.45 part of the fluorinated acetylene alcohol represented by the formula (10) in Example 1. A composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[Example 6]
Instead of 0.45 part of the fluorinated acetylene alcohol represented by the formula (10) of Example 1, 0.60 part of the fluorinated acetylene alcohol represented by the formula (16) of Example 4 and the formula (13) of Example 1 A composition was prepared in the same manner as in Example 1 except that 3.0 parts of the adhesion imparting agent represented by the following formula (18) was used instead of the adhesion imparting agent represented by: Evaluation was performed. The results are shown in Tables 1 and 2.

[Comparative Example 1]
Instead of 0.45 part of the fluorine-containing acetylene alcohol represented by the formula (10) of Example 1, 0.15 part of an isocyanurate represented by the following formula (19) and a toluene solution of an acetylene alcohol represented by the formula (20) ( 50% by mass) A composition was prepared in the same manner as in Example 1 except that 0.30 part was used, and the same evaluation as in Example 1 was performed (excluding the tensile shear adhesion test). The results are shown in Table 3.

[Comparative Example 2]
Instead of 0.45 part of the fluorine-containing acetylene alcohol represented by the formula (10) of Example 1, 0.12 part of an isocyanurate represented by the following formula (21) and a toluene solution of an acetylene alcohol represented by the formula (20) ( 50% by mass) A composition was prepared in the same manner as in Example 1 except that 0.30 part was used, and the same evaluation as in Example 1 was performed (excluding the tensile shear adhesion test). The results are shown in Table 3.

[Comparative Example 3]
Instead of 0.45 part of the fluorine-containing acetylene alcohol represented by the formula (10) of Example 1, 0.30 part of a toluene solution (50% by mass) of acetylene alcohol represented by the formula (20) of Comparative Example 1 was used. Except for the above, a composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1 (excluding the tensile shear adhesion test). The results are shown in Table 3.

Claims (4)

(A) 100 parts by mass of a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain;
(B) Fluorinated organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule (A) 0.5 to 3.0 moles as Si-H groups per mole of alkenyl groups in component (A) The amount,
(C) Platinum group metal hydrosilylation catalyst
0.1 to 500 ppm in terms of platinum group metal atoms,
(D) 0.5-30 parts by mass of hydrophobic silica powder,
(E) Fluorine-containing acetylene alcohol represented by the following general formula (2) or (3)
0.05-3.0 parts by mass,

(In the formula, Rf ² is a C 3-100 perfluoroalkyl group which may contain an ether bond in the middle or may be branched. Q is a C 1-6 divalent hydrocarbon. R ³ , R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms, which may be the same or different, and T is a divalent organic group having 1 to 20 carbon atoms.
(F) Organosiloxane having one or more hydrogen atoms directly bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms in one molecule. .1-10 parts by mass of an adhesive composition, The component (A) is represented by the following general formula (1):
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2 (1)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- (Y is -CH ₂ - or the following structural formula (Z)

O, m or a p-dimethylsilylphenylene group represented by formula (I), R ¹ is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (Y ′ is —CH ₂ — or the following structural formula (Z ′)

O, m or p-dimethylsilylphenylene group represented by formula (I), and R ² is the same group as R ¹ described above. Rf ¹ represents the following general formula (i) or (ii)

(In the formula, p and q are each an integer of 1 to 150, and the average of the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3. .)

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)
It is a bivalent perfluoropolyether group represented by these. a is independently 0 or 1. ]
The adhesive composition according to claim 1, which is a linear polyfluoro compound having a branch represented by the formula:   The component (B) fluorine-containing organohydrogensiloxane is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoroalkyl group in one molecule. The adhesive composition according to claim 1 or 2, which has a fluorooxyalkylene group. The (F) component organosiloxane further has a monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom. The adhesive composition according to any one of claims 1 to 3 , wherein the adhesive composition has one or more.